TW201434997A - Coloring composition, coloring cured film, display element, and solid-state imaging element - Google Patents

Abstract

[Problem to be solved] To provide a coloring composition suitable for forming a coloring cured film with high brightness and high coloring power. [Solution] A coloring composition comprises (A) a coloring agent, (B) an adhesive resin and (C) a polymerizable compound and is characterized by containing C.I. pigment Red 264 and isoindoline-based pigment as the coloring agent (A).

Description

Coloring composition, coloring cured film, display element, and solid-state imaging element

The present invention relates to a coloring composition, a colored cured film, a display element, and a solid-state imaging element, and more particularly to a color-type liquid crystal display element, a solid-state imaging element, an organic EL display element, and an electron for use in a transmissive or reflective type. A colored composition of a colored cured film used for paper or the like, a colored cured film formed using the colored composition, and a display element and a solid-state imaging element including the colored cured film.

A method for obtaining pixels of respective colors is disclosed in which a pigment-dispersed color-sensing radiation-linear composition is applied onto a substrate and dried, and then dried by applying a colored filter. The film is irradiated with radiation (hereinafter referred to as "exposure") in a desired pattern shape and developed (for example, refer to Patent Documents 1 and 2). Further, a method of forming a black matrix by using a photopolymerizable composition in which carbon black is dispersed is also known (for example, see Patent Document 3). Further, a method of obtaining a pixel of each color by an inkjet method using a pigment dispersion type colored resin composition is also known (for example, refer to Patent Document 4).

For display elements, in recent years, it has been required to increase the brightness and enlarge the color reproduction range. Therefore, it is required to have high luminance and high color purity for the coloring composition used for forming the pixel of the display element and forming the black matrix or the like. In solid-state photographic components, The colored pixel of the element is required to have an ultra-thin film having a film thickness of 1 μm or less and having a coloring power with high color purity. In response to such a request, a coloring composition containing C.I. Pigment Red 264 is proposed as a coloring composition capable of producing a color filter having high color purity (for example, see Patent Document 5).

Advanced technical literature Patent literature

Patent Document 1 JP-A-2-144502

Patent Document 2 Japanese Patent Publication No. 3-53201

Patent Document 3, JP-A-6-35188

Patent Document 4, JP-A-2000-310706

Patent Document 5 Japanese Patent Laid-Open No. Hei 10-300920

However, even with such a coloring composition, there is still a limit in the improvement of chromaticity characteristics. Therefore, it is strongly demanded to develop a coloring composition suitable for forming a colored cured film having higher brightness and high color purity.

Therefore, an object of the present invention is to provide a coloring composition suitable for forming a colored cured film having high brightness and high coloring power. Further, another object of the present invention is to provide a colored cured film formed using the colored composition, a display element including the colored cured film, and a solid-state imaging element.

As a result of intensive research by the inventors of the present invention, it has been found that the above problems can be solved by using a specific coloring agent.

That is, the present invention provides a coloring composition comprising (A) a coloring agent, (B) a binder resin, and (C) a coloring composition of a polymerizable compound, characterized in that: (A) a coloring agent is included CI Pigment Red 264, and isoporphyrin pigments.

Moreover, the present invention also provides a colored cured film formed using the above colored composition, and a display element and a solid-state imaging element including the colored cured film. Here, the "stained cured film" means a color pixel, a black matrix, a black spacer, or the like used in a display element and a solid-state imaging element.

By using the coloring composition of the present invention, a coloring layer having high brightness and high coloring power can be formed.

Therefore, the coloring composition of the present invention can be excellently used for production of solid-state imaging elements such as color liquid crystal display elements, organic EL display elements, display elements such as electronic paper, and CMOS image sensors.

Fig. 1 is a view showing an emission spectrum of a white LED obtained by mixing colors of a blue LED and a YAG-based phosphor used in the examples.

Fig. 2 is an emission spectrum chart showing a three-wavelength LED (a white LED obtained by combining a blue LED, a red luminescent phosphor, and a green luminescent phosphor and mixing them) used in the embodiment.

[Formation of the Invention]

The invention is described in detail below.

Coloring composition

The constituent components of the colored composition of the present invention will be described in detail below.

- (A) colorant -

The coloring composition of the present invention contains C.I. Pigment Red 264 and an isoporphyrin pigment as (A) coloring agent. Examples of the isoporphyrin pigment include C.I. Pigment Yellow 139, C.I. Pigment Yellow 185, and the like. Among them, preferred is C.I. Pigment Yellow 185.

(A ¹ ) The mass ratio [(A ¹ )/(A ² )] of the CI Pigment Red 264 to the (A ² )isoporphyrin pigment can be appropriately selected, and from the viewpoint of further enhancing the brightness and the coloring power. Preferably, the mass ratio [(A ¹ )/(A ² )]=99/1~50/50, more preferably 90/10~60/40, and even more preferably 85/15~70/30.

The colored composition of the present invention can be further used by mixing a coloring agent other than C.I. Pigment Red 264 and an isoporphyrin pigment. The other coloring agent is not particularly limited, and the color and the material can be appropriately selected depending on the application.

Examples of the other coloring agent include a pigment, a dye, and a natural coloring matter, and other coloring agents can be used alone or in combination of two or more. Among them, in order to obtain a pixel having high brightness, contrast, and coloring power, the pigment is preferably an organic pigment, and the dye is preferably an organic dye.

As the organic pigment, for example, a compound classified as a pigment in a color index (C.I.; issued by The Society of Dyers and Colourists), that is, a color index (C.I.) number as given below can be cited.

Red pigment other than CI Pigment Red 264 such as CI Pigment Red 166, CI Pigment Red 177, CI Pigment Red 179, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, etc.; CI Pigment Green 7, CI Pigment Green 36, Green pigment such as CI Pigment Green 58; blue pigment of CI Pigment Blue 15:6, CI Pigment Blue 16, CI Pigment Blue 80, etc.; CI Pigment Yellow 83, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 150 , a yellow pigment other than the isoporphyrin system such as CI Pigment Yellow 179, CI Pigment Yellow 180, CI Pigment Yellow 211, CI Pigment Yellow 215, etc.; an orange pigment such as CI Pigment Orange 38; and a violet pigment such as CI Pigment Violet 23.

In addition, it is described in JP-A-2001-081348, JP-A-2010-026334, JP-A-2010-191304, JP-A-2010-237384, JP-A-2010-237569 A lake pigment such as JP-A-2011-145346.

Further, as the dye, it is preferably A dye, a triarylmethane dye, a cyanine dye, an anthraquinone dye, an azo dye, or the like. More specifically, it is described in JP-A-2010-32999, JP-A-2010-254964, JP-A-2011-138094, International Publication No. 10/123071, and JP-A-2011-116803 An organic dye such as Japanese Laid-Open Patent Publication No. 2011-117987, and JP-A-2011-174987.

The pigment and the dye in the present invention may be used alone or in combination of two or more.

In the present invention, CI Pigment Red 264, isoporphyrin pigment, and other pigments which are optionally mixed may be recrystallized, reprecipitated, solvent washed, sublimed, vacuum heated or a combination thereof. Refined for use. Further, these pigments may also be used by modifying the surface of the particles with a resin as desired. Examples of the resin which is used to modify the surface of the pigment particles include a carrier resin described in JP-A-2001-108817 or a commercially available resin for pigment dispersion. For example, a method of coating a surface of a carbon black, for example, is disclosed in, for example, JP-A-H09-71733, JP-A-9-95625, and JP-A-9-124969. Further, the organic pigment may be used by refining the primary particles by a so-called salt milling. As a method of salt milling, for example, a method disclosed in Japanese Laid-Open Patent Publication No. Hei 08-179111 can be employed.

Further, in the present invention, a widely known dispersant and dispersing aid may be further contained together with C.I. Pigment Red 264, an isoporphyrin pigment, and other colorants which are optionally mixed. The well-known dispersing agent is exemplified by a urethane-based dispersing agent, a polyethyleneimine-based dispersing agent, a polyoxyethylene alkyl ether-based dispersing agent, and a polyoxyethylene alkyl phenyl ether-based dispersion. Agent, polyethylene glycol diester dispersant, sorbitan fatty acid ester dispersant, polyester dispersant, (meth)acrylic dispersant, etc., and as a dispersing aid, a pigment derivative is exemplified. Wait. Here, "(meth)acrylic" means either or both of "acrylic acid" and "methacrylic acid".

Such a dispersing agent can be obtained commercially. For example, as a (meth)acrylic dispersing agent, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK), etc. may be mentioned. Examples of the urethane-based dispersing agent include Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, BYK), and Solsperse 76500 (Lubrizol ( As a polyethyleneimine-based dispersing agent, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.) or the like is exemplified, and examples of the polyester-based dispersing agent include AJISPER PB821, AJISPER PB822, AJISPER PB880, and AJISPER. PB881 (above is Ajinomoto Fine-Techno Co., Ltd.) and the like.

Among such dispersants, a (meth)acrylic dispersant is preferred.

As the (meth)acrylic dispersant, a (meth)acrylic dispersant having a crosslinkable functional group in addition to a commercially available (meth)acrylic dispersant is also preferable. Examples of the crosslinkable functional group include an oxygen-containing saturated heterocyclic group such as an oxiranyl group, an oxycyclobutane group, a tetrahydrofuranyl group or a tetrahydropyranyl group, an ethylenically unsaturated group or an alkylthio group. , dithiocarbonate group and the like. Among these crosslinkable functional groups, an oxygen-containing saturated heterocyclic group is preferred, and an oxygen cyclobutane group or a tetrahydrofuranyl group is more preferred. In particular, the (meth)acrylic dispersing agent having a crosslinkable functional group can be synthesized by a method described in JP-A-2012-118505.

By such an aspect, the desired effect of the present invention can be obtained more.

Further, specific examples of the pigment derivative include a copper phthalocyanine, a diketopyrrolopyrrole, and a sulfonic acid derivative of quinoline yellow.

The colored composition of the present invention is generally used for the formation of red pixels, but C.I. Pigment Red 264 and isoporphyrin pigments may also be used in combination with other colorants. In this case, as the other coloring agent, a red coloring agent other than C.I. Pigment Red 264 is preferable, and particularly preferably C.I. Pigment Red 177 is contained.

The content ratio of the other coloring agent is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less based on the total amount of the coloring agent. The lower limit value is not particularly limited, and may be 0.01% by mass or more. In particular, when C.I. Pigment Red 177 is contained as the other coloring agent, the lower limit of the content ratio of C.I. Pigment Red 177 is preferably 20% by mass or more, and more preferably 30% by mass or more based on the total content of the coloring agent.

The colored composition of the present invention can be preferably used for the formation of a colored cured film which is a chromaticity coordinate (x, y) in an XYZ color chromaticity diagram measured by a 2 degree field of view using a C light source. It becomes 0.660≦x≦0.690 and 0.300≦y≦0.320. From the viewpoint of further improving the chromaticity characteristics, the lower limit value of the chromaticity coordinate value x is preferably 0.665, more preferably 0.668, and the upper limit of x is preferably 0.688, more preferably 0.686, and even more preferably 0.682. Further, the lower limit value of the chromaticity coordinate value y is preferably 0.302, more preferably 0.304, still more preferably 0.308, and the upper limit of y is preferably 0.318, more preferably 0.315.

Further, the coloring composition of the present invention can be preferably used for the formation of a colored cured film which has a chromaticity coordinate (x, y) in an XYZ color chromaticity diagram measured by a white LED, and is also 0.660. ≦x≦0.690 and 0.300≦y≦0.320.

In the case where the colored composition of the present invention is used for a colored cured film of a display element, (A) the content of the colorant in the solid content of the colored composition is from a pixel having high luminance and excellent tinting strength, or shading The point of the excellent black matrix is usually 5 to 70% by mass, preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and particularly preferably 20 to 50% by mass. In the coloring composition of the present invention, even when the content of the coloring agent (A) is 40% by mass or less, and further 30% by mass or less, particularly 25% by mass or less, high-brightness can be produced. A colored hardening film with high tinting strength.

In the case where the coloring composition of the present invention is used in a colored cured film of a solid-state image sensor, (A) the content ratio of the coloring agent is from the viewpoint of forming a pixel pattern excellent in color separation property and suppressing development residue. The solid content of the coloring composition is usually 30% by mass or more, preferably 40% by mass or more, more preferably 45% by mass or more, and particularly preferably 50% by mass or more. On the other hand, the upper limit is usually 70% by mass or less from the viewpoint of suppression of development residue and formation of a favorable pattern. Here, the "solid component" is a component other than the solvent described later.

- (B) Adhesive Resin -

The (B) binder resin of the present invention is not particularly limited, and is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter also referred to as "carboxy group-containing polycondensation" is preferred. ")", for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter also referred to as "unsaturated monomer (b1)") and other copolymerizable ethylenically unsaturated monomers (hereinafter also referred to as It is a copolymer of "unsaturated monomer (b2)").

Examples of the unsaturated monomer (b1) include (meth)acrylic acid, maleic acid, maleic anhydride, and succinic acid mono [2-(methyl) propylene oxyethyl ester]. Ω-carboxypolycaprolactone mono(meth)acrylate, p-vinylbenzoic acid, and the like.

These unsaturated monomers (b1) can be used alone or in combination of two or more.

Further, examples of the unsaturated monomer (b2) include N-position substituted maleidene such as N-phenylmaleimide and N-cyclohexylmethyleneimine. An amine; an aromatic vinyl compound such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyloxypropyl ether, vinyl naphthalene; Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, ( Methyl methacrylate, polyethylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) methyl ether (meth) acrylate, polyethyl b Glycol (degree of polymerization 2~10) mono (meth) acrylate, polypropylene glycol (degree of polymerization 2~10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isophthalic acid (meth) acrylate Ester, tricyclo[methyl]acrylic acid [5.2.1.0 ^2,6 ]decane-8-ester, dicyclopentadienyl (meth)acrylate, glycerol mono(meth)acrylate, (methyl) 4-hydroxyphenyl acrylate, pair Ethylene oxide modified (meth) acrylate of phenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, 3-[(meth) propylene (meth) acrylate of methoxymethyl] oxocyclobutane, 3-[(meth) propylene methoxymethyl]-3-ethyloxycyclobutane; such as cyclohexyl vinyl ether, isoindole Vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl vinyl ether, pentacyclopentadecyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxycyclobutane a vinyl ether; such as polystyrene, poly(methyl) methacrylate, poly(methyl) methacrylate, polyoxyalkylene having a mono (meth) acrylonitrile group at the end of the polymer molecular chain Giant molecular monomer and the like.

These unsaturated monomers (b2) can be used individually or in mixture of 2 or more types.

In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass, and more preferably 10%. 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a coloring composition excellent in alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. The copolymer disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

In the present invention, for example, Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylonitrile group in a side chain disclosed in JP-A-2008-181095, and the like is used as a binder resin.

In the binder resin of the present invention, the weight average molecular weight (Mw) of the converted polystyrene measured by gel permeation chromatography (hereinafter referred to as GPC) (solvent solvent: tetrahydrofuran) is usually 1,000 to 100,000, preferably 3,000. ~50,000. According to this aspect, the residual film ratio, the pattern shape, the heat resistance, the electrical characteristics, and the resolution of the film can be further improved, and the generation of dry foreign matter during coating can be suppressed at a high level.

Further, in the present invention, the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the binder resin is preferably from 1.0 to 5.0, more preferably from 1.0 to 3.0. Here, the Mn referred to herein is a number average molecular weight of converted polystyrene measured by GPC (solution solvent: tetrahydrofuran).

The adhesive resin of the present invention can be produced by a known method, for example, by the method disclosed in Japanese Laid-Open Patent Publication No. 2003-222717, JP-A-2006-259680, and International Publication No. 07/029871. It can also inhibit its structure and Mw, Mw / Mn.

In the present invention, the binder resin can be used singly or in combination of two or more.

In the present invention, the content of the binder resin is usually 10 to 1,000 parts by mass, preferably 20 to 500 parts by mass, per 100 parts by mass of the (A) colorant. By setting it as such an aspect, the alkali developability, the storage stability of a coloring composition, and a chromaticity characteristic can further be improved.

- (C) Polymeric Compound -

The polymerizable compound in the present invention means a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxycyclobutane group, and an N-alkoxymethylamino group. In the present invention, the polymerizable compound is preferably a compound having two or more (meth)acrylinyl groups or a compound having two or more N-alkoxymethylamino groups.

Specific examples of the compound having two or more (meth) acrylonitrile groups include polyfunctional (meth) acrylates and caprolactone obtained by reacting an aliphatic polyhydroxy compound with (meth)acrylic acid. A polyfunctional urethane obtained by reacting a modified polyfunctional (meth) acrylate, an alkylene oxide-modified polyfunctional (meth) acrylate, a hydroxyl group-containing (meth) acrylate, and a polyfunctional isocyanate ( A polyfunctional (meth) acrylate having a carboxyl group obtained by reacting a methyl acrylate, a (meth) acrylate having a hydroxyl group, and an acid anhydride.

Here, examples of the aliphatic polyhydroxy compound include a 2-membered aliphatic polyhydroxy compound such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; for example, glycerin, trimethylolpropane, and neopentyl An aliphatic polyhydroxy compound having 3 or more elements of tetraol or dipentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, trimethylolpropane di(meth)acrylate, and pentaerythritol tri(meth)acrylic acid. Ester, dipentaerythritol penta (meth) acrylate, glycerol dimethacrylate, and the like. Examples of the polyfunctional isocyanate include methylphenyl diisocyanate, exohexyl diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. The acid anhydride may, for example, be an anhydride such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride or hexahydrophthalic anhydride, such as 1,2. 4,5-benzenetetracarboxylic anhydride, biphenyltetracarboxylic dianhydride, diphenyl ketone tetracarboxylic acid dianhydride tetrabasic dianhydride.

In addition, examples of the caprolactone-modified polyfunctional (meth) acrylate include the compounds described in paragraphs [0015] to [0018] of JP-A-11-44955. The alkylene oxide-modified polyfunctional (meth) acrylate may, for example, be bisphenol A di(meth)acrylic acid modified by at least one selected from the group consisting of ethylene oxide and propylene oxide. An ester, at least one modified isocyanuric acid tri(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide, at least 1 selected from the group consisting of ethylene oxide and propylene oxide Modified trimethylolpropane tri(meth)acrylate, modified by at least one selected from ethylene oxide and propylene oxide, neopentyl alcohol tri(meth)acrylate At least one modified pentaerythritol tetra(meth)acrylate selected from the group consisting of ethylene oxide and propylene oxide, modified by at least one selected from the group consisting of ethylene oxide and propylene oxide The bis-pentaerythritol penta (meth) acrylate is modified by at least one selected from the group consisting of ethylene oxide and propylene oxide, such as dipentaerythritol hexa(meth)acrylate.

Further, examples of the compound having two or more N-alkoxymethylamino groups include a melamine structure and a benzoquinone structure. Structure, compound of urea structure, and the like. Among them, melamine structure, benzoquinone Structure means that there are more than one three Ring or benzene substituted three The chemical structure of the ring as a basic skeleton also contains melamine and benzoquinone. Or the concept of its condensate. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N', N', N", N"-hexa(alkoxymethyl) melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoquinone , N, N, N', N'-tetrakis(alkoxymethyl)acetylene urea, and the like.

Among these polymerizable compounds, a polyfunctional (meth) acrylate or a caprolactone-modified polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound having 3 or more members with (meth)acrylic acid is preferred. Ester, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate with carboxyl group, N, N, N', N', N", N"-hexa (alkoxy group) Melamine, N,N,N',N'-tetrakis(alkoxymethyl)benzoquinone . Among the polyfunctional (meth) acrylates obtained by reacting an aliphatic polyhydroxy compound of 3 or more elements with (meth)acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentane a compound obtained by reacting neopentyl alcohol triacrylate and succinic anhydride in a polyfunctional (meth) acrylate having a carboxyl group, and a neopentyl pentaacrylate, and a neopentyl alcohol hexaacrylate The compound obtained by reacting pentaerythritol pentaacrylate with succinic anhydride has high strength of the colored layer and excellent surface smoothness of the colored layer, and is less likely to generate scum and residual film on the unexposed portion of the substrate and the light shielding layer. It is especially good for points.

In the present invention, the (C) polymerizable compound can be used singly or in combination of two or more.

In the present invention, the content of the (C) polymerizable compound is preferably 10 to 1,000 parts by mass, more preferably 20 to 700 parts by mass, even more preferably 100 to 500 parts by mass per 100 parts by mass of the (A) coloring agent. Share. According to this aspect, the curability and the alkali developability can be further improved, and generation of scum, residual film, or the like on the substrate of the unexposed portion or the light shielding layer can be suppressed at a high level.

-Photopolymerization initiator -

A photopolymerization initiator may be included in the color composition of the present invention. Thereby, the coloring composition can be imparted with radiation. The photopolymerization initiator used in the present invention is a compound which can generate an active species capable of starting polymerization of the above polymerizable compound by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam or X-ray.

As such a photopolymerization initiator, for example, 9-oxygen sulfur can be cited. Compound, acetophenone compound, biimidazole compound, three Compound, O-mercapto oxime compound, sulfonium salt compound, benzoin compound, diphenyl ketone compound, α-diketone compound, polynuclear oxime compound, diazo compound, sulfimine sulfonate An acid salt compound or the like.

In the present invention, the photopolymerization initiator can be used singly or in combination of two or more. As the photopolymerization initiator, it is preferably selected from the group consisting of 9-oxosulfur Compound, acetophenone compound, biimidazole compound, three At least one of the group of the compound and the O-mercapto lanthanide compound.

In the preferred photopolymerization initiator of the present invention, as 9-oxygen sulfur Specific examples of the compound can be exemplified by 9-oxosulfur 2-chloro-9-oxosulfur 2-methyl-9-oxosulfur 2-isopropyl-9-oxosulfur 4-isopropyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 2,4-dimethyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-diisopropyl-9-oxosulfur Wait.

Further, specific examples of the acetophenone-based compound include 2-methyl-1-[4-(methylthio)phenyl]-2- Tropicpropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Phenylphenyl)butan-1-one, 2-(4-methylbenzyl)-2-(dimethylamino)-1-(4- Phenylphenyl)butan-1-one and the like.

Further, specific examples of the biimidazole-based compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-linked. Imidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2, 4,6-Trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole.

Among them, in the case where a biimidazole compound is used as a photopolymerization initiator, it is preferred to use a hydrogen donor in terms of improving sensitivity. The term "hydrogen donor" as used herein means a compound capable of supplying a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include 2-mercaptobenzothiazole and 2-mercaptobenzoene. An amine-based hydrogen donor such as a thiol-based hydrogen donor such as oxazole, 4,4'-bis(dimethylamino)diphenyl ketone or 4,4'-bis(diethylamino)diphenyl ketone . In the present invention, the hydrogen donor can be used singly or in combination of two or more. Among them, a combination of one or more kinds of thiol-based hydrogen donors and one or more kinds of amine-based hydrogen donors can be used to further improve the sensitivity.

Again, as the above three Specific examples of the compound include 2,4,6-paran (trichloromethyl)-s-three. 2-methyl-4,6-bis(trichloromethyl)-s-three ,2-[2-(5-methylfuran-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(furan-2-yl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(4-diethylamino-2-methylphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three ,2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-three , 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-three , 2-(4-ethoxystyryl)-4,6-bis(trichloromethyl)-s-three ,2-(4-n-butoxyphenyl)-4,6-bis(trichloromethyl)-s-three Three of the halomethyl groups a compound.

Further, specific examples of the O-fluorenyl fluorene-based compound include 1-[4-(phenylthio)phenyl]-1,2-octanedione 2-(O-benzamide), Ethyl ketone-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl]-1-(O-acetamidine), ethyl ketone-1-[ 9-Ethyl-6-(2-methyl-4-tetrahydrofuranmethoxybenzylidene)-9H-indazol-3-yl]-1-(O-acetamidine), ethyl ketone-1- {9-Ethyl-6-[2-methyl-4-(2,2-dimethyl-1,3-dioxolan)methoxybenzylidene]-9H-indazole-3- Base}-1-(O-acetamidine) and the like. As a commercial item of the O-mercapto fluorene-based compound, NCI-831, NCI-930 (above, ADEKA Co., Ltd.), DFI-020, DFI-091 (above, DAITO CHEMIX Co., Ltd.), etc. can be used. .

In the present invention, in the case of using a photopolymerization initiator other than the biimidazole compound such as an acetophenone-based compound, a sensitizer may be used in combination. Examples of such a sensitizer include 4,4′-bis(dimethylamino)diphenyl ketone, 4,4′-bis(diethylamino)diphenyl ketone, and 4-diethylamine. Acetophenone, 4-dimethylaminopropione, ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis(4-di Ethylbenzylidenemethyl)cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzimidyl) humectin, 4-(diethylamino)chalcone, and the like.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass, per 100 parts by mass of the (C) polymerizable compound. By setting this aspect, the hardenability and film characteristics can be further improved.

- solvent -

The colored composition of the present invention contains the above components (A) to (C) and any other components added arbitrarily. However, it is usually prepared by mixing a solvent into a liquid composition.

The solvent is appropriately selected and used as long as it disperses or dissolves the components (A) to (C) constituting the colored composition and does not react with these components, and has moderate volatility.

Examples of such a solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol monomethyl. Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol (poly)alkylene glycol monoalkyl ethers such as mono-n-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether; alkyl lactate such as methyl lactate or ethyl lactate; methanol , (cyclo)alkyl alcohols such as ethanol, propanol, butanol, isopropanol, isobutanol, tertiary butanol, octanol, 2-ethylhexanol, cyclohexanol; diacetone alcohol, etc. Keto alcohols; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, Propylene glycol monomethyl ether Ester, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, etc. a diol monoalkyl ether acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran or the like; Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc.; propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, etc. Diacetate; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethoxyacetic acid Alkoxycarboxylates such as ethyl ester, 3-methyl-3-methoxybutyl propionate; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate , n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, Other esters such as n-propyl pyruvate, methyl acetoacetate, ethyl acetate, ethyl 2-oxobutanoate, aromatic hydrocarbons such as toluene and xylene; N,N-dimethyl A decylamine such as formamide, N,N-dimethylacetamide or N-methylpyrrolidone or an indoleamine.

Among these solvents, from the viewpoints of solubility, pigment dispersibility, coatability and the like, (poly)alkylene glycol monoalkyl ethers, alkyl lactates, (poly)alkylene glycols are preferred. Monoalkyl ether acetates, other ethers, ketones, diacetates, alkoxycarboxylates, other esters, particularly preferably propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol Monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl Ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, ethyl lactate, 3-methoxy Ethyl propyl propionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutyl propionate, n-butyl acetate, isobutyl acetate Formic acid N-amyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl butyrate, n-butyl butyrate, ethyl pyruvate, and the like.

In the present invention, the solvent may be used singly or in combination of two or more. In the case of mixed use, it is preferred to at least (poly)alkylene glycol monoalkyl ethers and (poly)alkylene glycol monoalkyl ether acetates, (poly)alkylene glycol monoalkyl ether acetates Used in combination with alkoxycarboxylic acid esters.

The content of the solvent is not particularly limited, and the total concentration of each component other than the solvent for removing the coloring composition is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. By setting it as such a form, the coloring agent dispersion liquid which is excellent in dispersibility and stability, and the coloring composition which is excellent in applicability and stability can be obtained.

-additive-

The colored composition of the present invention can contain various additives as needed.

The additive may, for example, be a filler such as glass or alumina; a polymer compound such as polyvinyl alcohol or poly(fluoroalkyl acrylate); or a surfactant such as a fluorine-based surfactant or a lanthanoid surfactant; Agent; vinyl trimethoxy decane, vinyl triethoxy decane, vinyl ginseng (2-methoxyethoxy) decane, N-(2-aminoethyl)-3-aminopropyl Dimethoxyoxane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyl Trimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethyl a adhesion promoter such as oxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane; 2,2-sulfuric double (4-methyl-6-tertiary butyl phenol), 2,6-di(tributyl)phenol, neopentyl quinone [3-(3,5-di(tri-butyl)-4) -hydroxyphenyl)propionate],3,9-bis[2-[3-(3-tri-butyl-4-hydroxy-5-methylphenyl)-propenyloxy]-1,1 -dimethyl Yl] -2,4,8,10-four Antioxidant such as spiro[5.5]undecane, thiodiethylidene bis[3-(3,5-di(tri-butyl)-4-hydroxyphenyl)propionate; 2-(3- a UV absorber such as a tertiary butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole or an alkoxydiphenyl ketone; a deflocculating agent such as sodium polyacrylate; Acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, Residual modifier for 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, etc.; succinic acid mono [2-(methyl) Development improver such as propylene oxime ethyl ester], fumaric acid mono [2-(methyl) propylene oxyethyl ester], ω-carboxy polycaprolactone mono (meth) acrylate Wait.

Among them, the coloring composition of the present invention preferably contains an antioxidant, more preferably a hindered phenol-based antioxidant, and particularly preferably contains neopentyl quinone [3-(3,5-di(tri-butyl)- 4-hydroxyphenyl)propionate].

The colored composition of the present invention can be prepared by an appropriate method, and can be prepared, for example, by mixing the components (A) to (C) with a solvent and optionally adding other components. Among them, a preferred method is to pulverize and mix/dispers a pigment in a solvent together with a part of the component (B) in the presence of a dispersing agent, for example, using a bead mill, a roll mill or the like as a pigment. In the dispersion of the pigment, the components (B) to (C) are added to the pigment dispersion, and a solvent and other components which are further added as needed are mixed and prepared.

Colored cured film and method of producing the same

The colored cured film of the present invention is formed using the colored composition of the present invention, and specifically means a color pixel, a black matrix, a black spacer, or the like used for a color filter.

The colored cured film used for the color filter and a method of forming the same will be described below.

As a method of manufacturing a color filter, the following method is mentioned first. First, a light shielding layer (black matrix) is formed on the surface of the substrate in such a manner as to form a portion where the pixels are formed. Next, on the substrate, for example, a red liquid composition of the radiation sensitive coloring composition of the present invention is applied, and then prebaked to evaporate the solvent to form a coating film. Next, the coating film was exposed through a photomask, and then developed using an alkali developing solution to dissolve and remove the unexposed portion of the coating film. Then, by post-baking, a red pixel pattern (colored cured film) forms a pixel array arranged in a predetermined arrangement.

Next, using each of the green or blue radiation-sensitive coloring compositions, coating, prebaking, exposing, developing, and post-baking the respective radiation-sensitive coloring compositions are performed in the same manner as described above, and green is sequentially formed on the same substrate. Pixel array and blue pixel array. Thereby, a color filter in which pixel arrays of three primary colors of blue, green, and red are arranged on the substrate is obtained. However, the order in which the pixels of the respective colors are formed in the present invention is not limited to the above.

Further, the black matrix can be formed by forming a desired pattern by photolithography using a metal thin film such as chromium which is formed by sputtering or vapor deposition, but a radiation-sensitive coloring composition in which a black pigment is dispersed can also be used. It is formed in the same manner as in the case of forming the above-described pixels.

Examples of the substrate used in forming the color filter include glass, ruthenium, polycarbonate, polyester, aromatic polyamine, polyamidimide, and polyimine.

Further, these substrates may be subjected to appropriate pretreatment such as drug treatment, plasma treatment, ion plating, sputtering, gas phase reaction, vacuum deposition, or the like, such as a decane coupling agent.

When the radiation sensitive coloring composition is applied onto a substrate, a spray coating method, a roll coating method, a spin coating method (spin coating method), a slit die coating method (slit coating method), or a bar coating method may be employed. A suitable coating method. Among them, a spin coating method or a slit die coating method is preferably used.

Prebaking is usually carried out by combining vacuum drying and heat drying. Drying under reduced pressure usually proceeds until it reaches 50 to 200 Pa. Further, the conditions for heating and drying are usually about 70 to 110 ° C for about 1 to 10 minutes.

The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, in terms of the film thickness after drying.

Examples of the light source for forming radiation used in at least one selected from the group consisting of a pixel and a black matrix include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, and a metal halide lamp. Light source such as mercury lamp, low-pressure mercury lamp, or laser source such as argon ion laser, YAG laser, XeCl excimer laser, and nitrogen laser. As the exposure light source, an ultraviolet LED can also be used. Radiation having a wavelength in the range of 190 to 450 nm is preferred.

The exposure amount of the radiation is generally preferably from 10 to 10,000 J/m ² . Further, as the alkali developing solution, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-azobiscyclo-[5.4.0 is preferable. An aqueous solution of 7-undecene, 1,5-azobicyclo-[4.3.0]-5-nonene or the like.

A water-soluble organic solvent such as methanol or ethanol or a surfactant may be added to the alkali developer in an appropriate amount. Among them, water is usually washed after alkali development.

As the development treatment method, a shower development method, a spray development method, a dip development method, a puddle development method, or the like can be applied. The developing conditions are preferably 5 to 300 seconds at normal temperature.

The post-baking conditions are usually about 10 to 60 minutes at 180 to 280 °C.

The film thickness of the pixel formed in this manner is usually 0.5 to 5 μm, preferably 1.0 to 3 μm.

Moreover, as a second method of producing a color filter, a method of obtaining pixels of respective colors by an inkjet method disclosed in Japanese Laid-Open Patent Publication No. Hei. No. Hei. In this method, first, a barrier wall having a light-shielding function is formed on the surface of the substrate. Next, a liquid composition of, for example, a blue thermosetting coloring composition of the present invention is discharged into the formed barrier wall by an inkjet device, and then prebaked to evaporate the solvent. Next, the coating film is exposed as needed, and then hardened by post-baking to form a blue pixel pattern.

Next, using each of the green or red thermosetting coloring composition, a green pixel pattern and a red pixel pattern were sequentially formed on the same substrate in the same manner as described above. Thereby, a color filter in which pixel patterns of three primary colors of blue, green, and red are arranged on the substrate is obtained. However, in the present invention, the order in which the pixels of the respective colors are formed is not limited to the above.

Among them, the barrier wall not only functions as a light-shielding function, but also functions as a thermosetting coloring composition for discharging the respective colors in the division, so that the film thickness is smaller than that of the black matrix used in the first method. Thicker. Therefore, the barrier walls are usually formed using a black sensitizing radioactive composition.

The method and conditions for pre-baking and post-baking of the substrate and the radiation source used in forming the color filter are the same as those of the first method described above. In this manner, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the barrier rib.

On the pixel pattern thus obtained, a protective film is formed as needed, and then a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but a spacer having a light-shielding property (black spacer) may also be used. In this case, a color-sensitive radiation composition in which a black coloring agent is dispersed is used, and the coloring composition of the present invention can also be applied to the formation of such a black spacer.

The colored composition of the present invention can also be applied to the formation of a colored cured film of any of the color pixels, the black matrix, the black spacer, and the like used in the above color filter.

The color filter including the colored cured film of the present invention formed in this manner has a high brightness and coloring power, and is applied to a color liquid crystal display element, a color image sensor element, a color sensor, an organic EL display element, an electronic paper, or the like. Extremely useful. Here, the display element to be described later may have at least one colored cured film formed using the colored composition of the present invention.

Display component

The display element of the present invention is provided with the colored cured film of the present invention. Examples of the display element include a color liquid crystal display element, an organic EL display element, and electronic paper.

The color liquid crystal display element having the colored cured film of the present invention may be of a transmissive type or a reflective type, and may have an appropriate structure. For example, a color filter may be formed on a substrate different from a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate on which the driving substrate and the color filter are formed may be opposed to each other through the liquid crystal layer. Further, a substrate in which a color filter is formed on a surface of a driving substrate on which a thin film transistor (TFT) is disposed, and an ITO (tin-doped indium oxide) electrode or IZO (indium oxide and zinc oxide) may be used. The mixture of the electrodes of the substrate, through the structure of the liquid crystal layer opposite. The structure of the latter can significantly increase the aperture ratio, and has the advantage of obtaining a bright and high-definition liquid crystal display element. In the case where the latter structure is employed, the black matrix and the black spacer may be formed on either the substrate side on which the color filter is formed and the substrate side on which the ITO electrode or the IZO electrode is formed.

A color liquid crystal display element having the colored cured film of the present invention may be provided with a backlight unit using a white LED as a light source in addition to a CCFL (Cold Cathode Fluorescent Lamp). As the white LED, for example, a white LED which is white light is obtained by combining a red LED, a green LED, and a blue LED; and a blue LED, a red LED, and a green phosphor are combined and mixed. And obtaining a white LED of white light; obtaining white by combining a blue LED, a red luminescent phosphor and a green luminescent phosphor and mixing colors a white LED for light; a white LED that is white light is obtained by mixing a blue LED with a YAG-based phosphor; by combining a blue LED, an orange-emitting phosphor, and a green-emitting phosphor, and mixing colors A white LED of white light is obtained; a white LED or the like of white light is obtained by combining an ultraviolet LED, a red luminescent phosphor, a green luminescent phosphor, and a blue luminescent phosphor and mixing colors.

The color liquid crystal display element having the colored cured film of the present invention can be applied to a TN (twisted nematic) type, an STN (super twisted nematic) type, an IPS (in-plane switching) type, a VA (vertical arrangement) type, and an OCB (optical). Appropriate liquid crystal mode for compensating for birefringence type or the like.

In addition, the organic EL display device having the colored cured film of the present invention can have an appropriate structure, and the structure disclosed in Japanese Laid-Open Patent Publication No. Hei 11-307242, for example.

Further, the electronic paper having the colored cured film of the present invention can have an appropriate structure, and a structure disclosed in, for example, JP-A-2007-41169 can be cited.

Solid state imaging element

The solid-state imaging element of the present invention comprises the colored cured film of the present invention. Further, the solid-state imaging element of the present invention can adopt a suitable structure. For example, in one embodiment, the colored composition of the present invention can be formed on a semiconductor substrate such as a CMOS substrate by forming a colored pixel (colored cured film) by the same operation as described above. Excellent solid-state photographic components.

[Example 1]

Hereinafter, embodiments of the present invention will be further specifically described by way of examples. However, the invention is not limited to the embodiments described below.

<Synthesis of Adhesive Resin> Synthesis Example 1

80 parts by mass of propylene glycol monomethyl ether acetate was placed in a flask equipped with a cooling tube and a stirrer, and nitrogen substitution was carried out. Heating to 80 ° C, 50 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 15 parts by mass of methacrylic acid 2- at the same temperature for 2 hours Hydroxyethyl ester, 38 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenyl maleimide and 15 parts by mass of succinic acid mono(2-propenyloxyethyl) a mixed solution of the ester), and a mixed solution of 20 parts by mass of propylene glycol monomethyl ether acetate and 6 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile), respectively. The polymerization was maintained at this temperature for 1 hour. Then, the temperature of the reaction solution was raised to 90 ° C, and further polymerization was carried out for 1 hour to obtain a resin (A-1) solution (solid content concentration = 40% by mass). The obtained resin (A-1) was Mw = 10,500, Mn = 5,900, and Mw / Mn = 1.78.

Synthesis Example 2

80 parts by mass of propylene glycol monomethyl ether acetate was placed in a flask equipped with a cooling tube and a stirrer, and nitrogen substitution was carried out. Heating to 80 ° C, 50 parts by mass of propylene glycol monomethyl ether acetate, 15 parts by mass of methacrylic acid, 10 parts by mass of styrene, and 12.5 parts by mass of methacrylic acid 2- at the same temperature for 3 hours Hydroxyethyl ester, 38 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenyl-butenylene a mixed solution of quinone imine and 12.5 parts by mass of succinic acid mono(2-propenyl oxirane ester), with 20 parts by mass of propylene glycol monomethyl ether acetate and 6 parts by mass of 2,2'-couple A mixed solution of nitrogen bis(2,4-dimethylvaleronitrile) was separately dropped, and polymerization was maintained at this temperature for 1 hour. Then, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour. Then, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added to adjust the solid content to 40% by mass to obtain a resin (A-2) solution (solid content concentration = 40% by mass). The obtained resin (A-2) was Mw = 10,800, Mn = 5,900, and Mw/Mn = 1.83.

Synthesis Example 3

80 parts by mass of propylene glycol monomethyl ether acetate was placed in a flask equipped with a cooling tube and a stirrer, and nitrogen substitution was carried out. Heating to 80 ° C, 50 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 10 parts by mass of styrene, 15 parts by mass of methacrylic acid 2- at the same temperature for 3 hours a mixture solution of hydroxyethyl ester, 29 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of N-phenyl maleimide and 14 parts by mass of methacrylic tea ester, and 20 masses A mixed solution of propylene glycol monomethyl ether acetate and 3 parts by mass of azobisisobutyronitrile was separately dropped, and polymerization was carried out at this temperature for 1 hour. Then, the temperature of the reaction solution was raised to 100 ° C, and further polymerization was carried out for 1 hour. Then, the mixture was cooled to room temperature, and propylene glycol monomethyl ether acetate was added to adjust the solid content concentration to 40% by mass to obtain a resin (A-3) solution (solid content concentration = 40% by mass). The obtained resin (A-3) was Mw = 9.70, Mn = 5,700, and Mw / Mn = 1.70.

<Synthesis of Dispersant> Synthesis Example 4

In a 1000 mL flask, 521.03 g of tetrahydrofuran (THF), 48.20 g of lithium chloride (3.59 mass% concentrated THF solution), and 2.11 g of diisopropylamine were added, and the mixture was cooled to -60 °C. Then, 8.67 g of n-butyllithium (15.36 mass% concentrated hexane solution) was added and cooked for 15 minutes.

Next, 44.75 g of dimethylaminoethyl methacrylate (DMMA) was added dropwise, and the reaction was continued for 20 minutes after the dropwise addition. Then, GC (gas chromatography) was measured to confirm the disappearance of the monomer. A portion of the reaction solution was sampled and analyzed by GPC (mobile phase THF, PMMA standard), molecular weight (Mw) was 3,060, and molecular weight distribution (Mw/Mn) was 1.09.

Next, 27.80 g of methyl methacrylate (MMA), 39.31 g of n-butyl methacrylate (nBMA), and 28.15 g of tetrahydrofurfuryl methacrylate (hereinafter also referred to as THFMA) were used for 60 minutes. The droplets were mixed in, and the reaction was continued for 30 minutes after the dropwise addition. After measuring the GC and confirming the disappearance of the monomer, 3.29 g of methanol was added to stop the reaction.

The copolymer obtained was analyzed by GPC (mobile phase DMF, PMMA standard), and had a molecular weight (Mw) of 9,020 and a molecular weight distribution (Mw/Mn) of 1.12. Further, the obtained copolymer was a block copolymer of DMMA-[MMA/nBMA/THFMA], and the composition ratio (% by mass) was confirmed to be DMMA/MMA/nBMA/THFMA=32/20/28/20.

The reaction solution was diluted with ethyl acetate, washed with water three times and then evaporated. After replacing propylene glycol monomethyl ether acetate as a solvent, propylene glycol monomethyl ether was added to adjust to propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 7 / 3 (w / w). Add 0.8 equivalent of chlorotoluene (BzCl) to DMMA, The tertiary metal structure was quaternized by reacting at 70 ° C for 7 hours. Finally, a resin solution (X-1) of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 7 / 3 (w / w) having a solid concentration of 40% by mass was obtained. This resin corresponds to a dispersant having a tetrahydrofuran group as a crosslinkable functional group.

<Preparation of Colorant Dispersion> Modulation example 1

10.7 parts by mass of CI Pigment Red 264, 2.3 parts by mass of CI Pigment Yellow 185 as a coloring agent, and 13.0 parts by mass of BYK-LPN21116 (manufactured by BYK Chemie (BYK) Co., Ltd.) as a dispersing agent (solid content concentration = 40 mass) %), 10.0 parts by mass of the resin (A-1) solution, 62.0 parts by mass of propylene glycol monomethyl ether acetate as a solvent, and 16.0 parts by mass of propylene glycol monoethyl ether, mixed/dispersed in a bead mill to prepare Red pigment dispersion (R-1).

Modulation example 2~13

The red pigment dispersion liquids (R-2) to (R-13) were prepared in the same manner as in Preparation Example 1 except that the type and amount of the coloring agent in the preparation example 1 were changed as shown in Table 1. In addition, in the preparation example 4 and the preparation examples 7 to 9, the coloring agents described in Table 1 were mixed at any ratio, and the chromaticity characteristics of the C light source and the white LED emission spectrum which will be described later could not be produced. In the evaluation, the chromaticity coordinate value satisfies the cured film of x ≧ 0.660 and y ≦ 0.320, so the modulation of the pigment dispersion is abandoned.

Modulation example 14

10.7 parts by mass of C.I. Pigment Red 264, 2.3 parts by mass of C.I. Pigment Yellow 185 as a coloring agent, and 4.0 parts by mass of BYK-LPN6919 (manufactured by BYK Chemie (BYK) Co., Ltd.) as a dispersing agent (solid) Component concentration = 60% by mass), 7.0 parts by mass of the resin solution (X-1) (solid content concentration = 40% by mass), 10.0 parts by mass of the resin (A-1) solution, and 64.0 parts by mass of the solvent as the solvent Methyl ether acetate and 16.0 parts by mass of propylene glycol monoethyl ether were mixed/dispersed in a bead mill to prepare a red pigment dispersion (R-14).

Modulation example 15

In the same manner as in Preparation Example 1, except that 8.8 parts by mass of C.I. Pigment Red 264 and 4.2 parts by mass of C.I. Pigment Yellow 185 were used as the coloring agent, a red pigment dispersion liquid (R-15) was prepared.

The components of Table 1 are as follows.

R264: C.I. Pigment Red 264

R254: C.I. Pigment Red 254

R242: C.I. Pigment Red 242

R177: C.I. Pigment Red 177

Y185: C.I. Pigment Yellow 185

Y139: C.I. Pigment Yellow 139

Y150: C.I. Pigment Yellow 150

Y129: C.I, Pigment Yellow 129

<Modulation and evaluation of coloring composition> Example 1 Modulation of coloring composition

624 parts by mass of a red pigment dispersion (R-1) as a colorant, 91 parts by mass of a resin (A-1) solution as a binder resin, and 90 parts by mass of dipentaerythritol as a polymerizable compound A mixture of hexaacrylate and dipentaerythritol pentaacrylate (Aronix M-402, manufactured by Toagosei Co., Ltd.), 4.0 parts by mass of Adeka arc Luz NCI-831 (ADEKA Co., Ltd.) as a photopolymerization initiator (manufactured by Irganox 1010, BASF), 1.0 parts by mass of neopentyl alcohol oxime [3-(3,5-di(tri-butyl)-4-hydroxyphenyl)propionate] as an antioxidant 9.7 parts by mass of a propylene glycol monomethyl ether acetate 5% by mass solution of MEGAFACE F-554 (manufactured by DIC Corporation) as a surfactant, and 321 parts by mass of propylene glycol monomethyl ether as a solvent 70 parts by mass of methoxybutyl acetate and 30 parts by mass of ethyl 3-ethoxypropionate were mixed to obtain a red colored composition (S-1) having a solid concentration of 20% by mass.

Evaluation of chromaticity characteristics

The red coloring composition (S-1) was applied onto a glass substrate using a spin coater, and then prebaked in a hot plate at 90 ° C for 1 minute to form three coating films having different film thicknesses.

Next, after cooling the substrate to room temperature, the coating film on the substrate was exposed to radiation including wavelengths of 365 nm, 405 nm, and 436 nm at a exposure amount of 600 J/m ² using a high-pressure mercury lamp without passing through a photomask. . Then, a developing solution containing a 0.04% potassium hydroxide aqueous solution at 23 ° C was discharged onto the coating film on the substrate at a developing pressure of 1 kgf/cm ² (nozzle aperture: 1 mm) to carry out shower development. Then, these substrates were washed with ultrapure water, air-dried, and then baked in a clean oven at 230 ° C for 20 minutes to prepare a red cured film.

For each of the obtained three cured films, a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.) was used, and a chromaticity coordinate (x, y) and a stimulus value (Y) in the CIE color system were measured by a C light source and a 2 degree field of view. ). From the measurement results, the chromaticity coordinate value y and the stimulation value (Y) when the chromaticity coordinate value x=0.675 are obtained. Further, the film thickness of the obtained cured film was measured using Alpha-Step IQ manufactured by KLA-Tencor. The evaluation results are shown in Table 2.

Among them, it can be said that the larger the stimulation value (Y), the higher the brightness, and the thinner the film thickness, the greater the coloring power of the colorant.

Examples 2 to 6 and Comparative Examples 1 to 9

The red colored composition (S-2) to (S-15) were prepared in the same manner as in Example 1 except that the type of the red pigment dispersion liquid in Example 1 was changed as shown in Table 2. Then, the obtained red coloring compositions (S-2) to (S-15) were subjected to the same evaluation as in Example 1. The results are shown in Table 2. However, in Comparative Examples 2, 5, 6, and 7, when the chromaticity coordinate value x = 0.675, y > 0.320, a cured film satisfying 0.300 ≦ y ≦ 0.320 could not be obtained.

Example 7

In addition to the three red cured films prepared by using the red colored composition (S-1) prepared in Example 1, the color mixture obtained by the blue LED and the YAG-based phosphor as shown in Fig. 1 was used. The white LED emission spectrum was measured in the same manner as in Example 1 except that the C light source was used as a light source, and the chromaticity coordinates (x, y) and the stimulation value (Y) were measured. From the measurement results, the chromaticity coordinate value y and the stimulation value (Y) when the chromaticity coordinate value x=0.663 are obtained. Further, the film thickness of the obtained cured film was measured using Alpha-Step IQ manufactured by KLA-Tencor. The evaluation results are shown in Table 3.

Examples 8 to 12 and Comparative Examples 10 to 18

The three red cured films prepared in Examples 2 to 6 and Comparative Examples 1 to 9 using the red colored compositions (S-2) to (S-15) were evaluated in the same manner as in Example 7. The results are shown in Table 3. But in Comparative Example 11, 14, 15 and 16 did not obtain a cured film of y ≦ 0.320 at a chromaticity coordinate value of x = 0.663.

Example 13

In addition to the three red cured films prepared in Example 1 using the red colored composition (S-1), a three-wavelength LED as shown in Fig. 2 was used (by blue LED, red luminescent fluorescent light) The chromaticity coordinates (x, y) and the stimulating value (Y) were measured in the same manner as in Example 1 except that the white LED emitted by combining the body and the green luminescent phosphor and the color spectrum were used as the light source instead of the C light source. . From the measurement results, the chromaticity coordinate value y and the stimulation value (Y) when the chromaticity coordinate value x=0.685 are obtained. Further, the film thickness of the obtained cured film was measured using Alpha-Step IQ manufactured by KLA-Tencor. The evaluation results are shown in Table 4.

Examples 14 to 18 and Comparative Examples 19 to 27

Three red cured films prepared by using the red colored compositions (S-2) to (S-15) prepared in Examples 2 to 6 and Comparative Examples 1 to 9 were evaluated in the same manner as in Example 13. The results are shown in Table 4. However, in Comparative Examples 20, 23, 24 and 25, a cured film of y ≦ 0.315 at a chromaticity coordinate value of x = 0.685 was not obtained.

<Preparation and evaluation of colored cured film for solid-state photographic elements> Modulation example 16 (Modulation of composition for forming a base film)

After nitrogen substitution in the flask, 200 parts by mass of a solution of 0.6 parts by mass of methyl 2-methoxypropionate dissolved in 2,2'-azobisisobutyronitrile was added. After further adding 37.5 parts by mass of butyl methacrylate and 62.5 parts by mass of glycidyl methacrylate, the mixture was stirred and heated at 70 ° C for 6 hours. After cooling, a resin solution containing a polymer was obtained.

Next, 33.3 parts by mass (containing 10 parts of the polymer) of the resin solution was diluted with 31.9 parts by mass of methyl 3-methoxypropionate and 3.4 parts by mass of propylene glycol monomethyl ether, and 0.3 parts by mass of 1 was added. , 2,4-benzenetricarboxylic acid, 0.5 parts by mass of 3-glycidoxypropyltrimethoxydecane, and 0.005 parts by mass of the trade name "FC-4432" (manufactured by Sumitomo 3M Co., Ltd.) were dissolved and prepared into A composition for forming a base film.

Example 19

8.8 parts by mass of CI Pigment Red 264 as a coloring agent, 2.2 parts by mass of CI Pigment Yellow 185, and 8.45 parts by mass of BYK-LPN21324 (manufactured by BYK Chemie (BYK) Co., Ltd.) as a dispersing agent (solid content concentration = 40 mass) %), 8.45 parts by mass of the resin (A-2) solution (solid content concentration = 40% by mass), 67.87 parts by mass of propylene glycol monomethyl ether acetate and 4.23 parts by mass of propylene glycol monoethyl ether as a solvent, It was mixed/dispersed in a bead mill to prepare a red pigment dispersion (R-16).

Next, 455 parts by mass of the above-prepared red pigment dispersion liquid (R-16) as a coloring agent, and 0.28 parts by mass of a resin (A-3) solution as a binder resin (solid content concentration = 40% by mass) 15.07 parts by mass of KAYARAD DPEA-12 (manufactured by Nippon Kayaku Co., Ltd., ethylene oxide-modified dipentaerythritol hexaacrylate) as a polymerizable compound, and 4.07 parts by mass as a photopolymerization initiator Adeka arc Luz NCI-930 (made by ADEKA Co., Ltd.), 0.02 parts by mass of Ftergent FTX-218 (manufactured by NEOS Co., Ltd.) as a fluorine-based surfactant, and propylene glycol monomethyl ether acetate were mixed and obtained. A red colored composition (S-16) having a solid content concentration of 20% by mass and a pigment concentration of 50% by mass.

Formation and evaluation of pixel patterns

The base film-forming composition was applied onto a 6-inch wafer by a spin coating method using an automatic coating and developing device (CLEAN TRACK, trade name "MARK-Vz" manufactured by Tokyo Electronics Co., Ltd.), and then 300 at 230 ° C. Baking was performed in seconds to form a base film having a film thickness of 0.6 μm.

The red coloring composition (S-16) was applied onto the base film by a spin coating method, and then prebaked at 90 ° C for 150 seconds to form a coating film having a film thickness of 0.75 μm. Then, the obtained substrate was cooled to room temperature, and a reduced projection exposure machine (NSR-2005i10D manufactured by Nikon Co., Ltd., lens numerical aperture = 0.63) was passed through the reticle to have a wavelength of 365 nm (i-line) and 30 to 500 mJ/ The exposure amount of cm ² was exposed to the coating film on the substrate at intervals of 10 mJ/cm ² . Next, in an automatic coating and developing apparatus, it was subjected to a liquid-coating development with a 0.05% aqueous solution of tetramethylammonium hydroxide for 90 seconds, and then washed with ultrapure water, spin-dried, and then subjected to 230 ° C for 300 seconds on a hot plate. Bake to form a red colored pattern.

The red colored pattern was confirmed to be an ultrathin film required for a solid-state image sensor, and the color separation property was excellent. Therefore, the coloring composition of the present invention can be said to be capable of producing a color filter having high color purity and suitable for solid-state imaging elements.

Example 20

8.8 parts by mass of CI Pigment Red 264 as a coloring agent, 2.2 parts by mass of CI Pigment Yellow 185, and 5.63 parts by mass of BYK-LPN6919 (manufactured by BYK Chemie (BYK) Co., Ltd.) as a dispersing agent (solid content concentration = 60 mass) %), 8.45 parts by mass of the resin (A-2) solution (solid content concentration = 40% by mass), and 70.69 parts by mass of the solvent as a solvent The diol monomethyl ether acetate and 4.23 parts by mass of propylene glycol monoethyl ether were mixed/dispersed in a bead mill to prepare a red pigment dispersion (R-17).

Next, in the same manner as in Example 19 except that the red pigment dispersion liquid (R-17) prepared above was used instead of the red pigment dispersion liquid (R-16), a solid content concentration of 20% by mass and a pigment concentration were obtained. 50% by mass of the red coloring composition (S-17). Then, a pixel pattern was formed in the same manner as in Example 19, and it was confirmed that the color separation property was excellent. Therefore, it can be said that a color filter having high color purity and suitable for solid-state imaging elements can be produced.

Claims (9)

A coloring composition comprising (A) a coloring agent, (B) a binder resin, and (C) a coloring composition of a polymerizable compound, wherein the coloring agent (A) contains CI Pigment Red 264, And isoporphyrin pigments. The coloring composition of claim 1, wherein the mass ratio of (A ¹ )CI Pigment Red 264 to (A ² )isoporphyrin pigment is [(A ¹ )/(A ² )] is 99/1 to 50 /50. The coloring composition of claim 1, wherein the isoindoline pigment is at least one selected from the group consisting of C.I. Pigment Yellow 139 and C.I. Pigment Yellow 185. The coloring composition of claim 1, wherein the coloring agent (A) further contains a red coloring agent other than C.I. Pigment Red 264. The coloring composition of claim 4, wherein the red coloring agent other than the C.I. Pigment Red 264 is C.I. Pigment Red 177. The colored composition according to any one of claims 1 to 5, which is used for forming a colored cured film having a chromaticity coordinate in an XYZ color chromaticity diagram measured by a C-light source in a 2 degree field of view ( x, y) is 0.660 ≦ x ≦ 0.690 and 0.300 ≦ y ≦ 0.320. A colored hardening film formed using the colored composition of any one of claims 1 to 6. A display element comprising the colored cured film of claim 7. A solid-state photographic element comprising the colored cured film of claim 7.